EP3376076A1 - Joint - Google Patents

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Publication number
EP3376076A1
EP3376076A1 EP17204605.4A EP17204605A EP3376076A1 EP 3376076 A1 EP3376076 A1 EP 3376076A1 EP 17204605 A EP17204605 A EP 17204605A EP 3376076 A1 EP3376076 A1 EP 3376076A1
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EP
European Patent Office
Prior art keywords
gasket
polymer chains
base material
group
gasket base
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP17204605.4A
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German (de)
English (en)
Inventor
Yasuhisa Minagawa
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Sumitomo Rubber Industries Ltd
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Sumitomo Rubber Industries Ltd
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Filing date
Publication date
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Publication of EP3376076A1 publication Critical patent/EP3376076A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/16—Sealings between relatively-moving surfaces
    • F16J15/32—Sealings between relatively-moving surfaces with elastic sealings, e.g. O-rings
    • F16J15/3284—Sealings between relatively-moving surfaces with elastic sealings, e.g. O-rings characterised by their structure; Selection of materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M5/00—Devices for bringing media into the body in a subcutaneous, intra-vascular or intramuscular way; Accessories therefor, e.g. filling or cleaning devices, arm-rests
    • A61M5/178—Syringes
    • A61M5/31—Details
    • A61M5/315—Pistons; Piston-rods; Guiding, blocking or restricting the movement of the rod or piston; Appliances on the rod for facilitating dosing ; Dosing mechanisms
    • A61M5/31511—Piston or piston-rod constructions, e.g. connection of piston with piston-rod
    • A61M5/31513—Piston constructions to improve sealing or sliding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F120/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J1/00—Pistons; Trunk pistons; Plungers
    • F16J1/001—One-piece pistons
    • F16J1/003—One-piece pistons with integral sealing lips
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/16—Sealings between relatively-moving surfaces
    • F16J15/32—Sealings between relatively-moving surfaces with elastic sealings, e.g. O-rings
    • F16J15/3204—Sealings between relatively-moving surfaces with elastic sealings, e.g. O-rings with at least one lip
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M2205/00—General characteristics of the apparatus
    • A61M2205/02—General characteristics of the apparatus characterised by a particular materials
    • A61M2205/0222—Materials for reducing friction
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2311/00—Characterised by the use of homopolymers or copolymers of chloroprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2323/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides
    • C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide

Definitions

  • the present invention relates to a gasket.
  • Patent Literature 2 a method of coating surfaces with a self-lubricating PTFE film has been proposed (see Patent Literature 2).
  • PTFE films are generally expensive and thus increase the production cost of processed products, limiting the range of application of the method.
  • products coated with PTFE films might be unreliable when they are used in applications where sliding or similar movement is repeated and durability is therefore required.
  • PTFE-coated products since PTFE is vulnerable to radiation, PTFE-coated products unfortunately cannot be sterilized by radiation.
  • the present invention aims to solve the above problems and provide a gasket excellent in properties such as sliding properties and resistance to liquid leakage.
  • the present invention relates a gasket, including a gasket base material whose surface is at least partially provided with immobilized polymer chains, the gasket having a sliding surface provided with multiple annular projections, the annular projections including a first projection nearest to a top surface of the gasket, the first projection having a surface roughness Ra of 1.0 or less.
  • the first projection has a surface roughness Ra of 0.8 or less.
  • the first projection has a surface roughness Ra of 0.6 or less.
  • the gasket base material has a surface roughness Ra of 1.0 or less.
  • the gasket base material has a surface roughness Ra of 0.8 or less.
  • the gasket base material has a surface roughness Ra of 0.6 or less.
  • the polymer chains are immobilized by a surface modification method I including: Step 1 of forming polymerization initiation points A on the surface of the gasket base material; and Step 2 of radically polymerizing a monomer starting from the polymerization initiation points A to grow polymer chains.
  • the surface modification method I includes: Step 3 of extending the polymer chains grown in Step 2 with the same type or a different type of polymer chain; or Step 3' of attaching a silane compound to surfaces of the polymer chains grown in Step 2, followed by reaction with a perfluoroether group-containing silane compound to grow functional polymer chains.
  • Step 1 includes adsorbing a photopolymerization initiator A onto the surface of the gasket base material, optionally followed by irradiation with LED light having a wavelength of 300 to 450 nm, to form polymerization initiation points A from the photopolymerization initiator A on the surface.
  • Step 2 includes radically polymerizing a monomer starting from the polymerization initiation points A by irradiation with LED light having a wavelength of 300 to 450 nm to grow polymer chains.
  • the polymer chains are immobilized by a surface modification method II including Step I of radically polymerizing a monomer in the presence of a photopolymerization initiator A on the surface of the gasket base material to grow polymer chains.
  • the surface modification method II includes: Step II of extending the polymer chains grown in Step I with the same type or a different type of polymer chain; or Step II' of attaching a silane compound to surfaces of the polymer chains grown in Step I, followed by reaction with a perfluoroether group-containing silane compound to grow functional polymer chains.
  • Step I includes radically polymerizing a monomer by irradiation with LED light having a wavelength of 300 to 450 nm to grow polymer chains.
  • the polymer chains have a length of 500 to 5,000 nm.
  • the gasket of the present invention includes a gasket base material whose surface is at least partially provided with immobilized polymer chains, the gasket having a sliding surface provided with multiple annular projections, the annular projections including a first projection nearest to the top surface of the gasket, the first projection having a surface roughness Ra of 1.0 or less.
  • the present invention provides a gasket excellent in properties such as sliding properties and resistance to liquid leakage without applying any sliding property-improving agent that can adversely affect chemical liquids, e.g., silicone oil, to the sliding surface.
  • the gasket of the present invention includes a gasket base material whose surface is at least partially provided with immobilized polymer chains. Further, the gasket has a sliding surface provided with multiple annular projections. Further, the multiple annular projections of the gasket include a first projection nearest to the top surface, and the first projection has a surface roughness Ra of 1.0 or less. Due to the polymer chains immobilized on the surface of the base material and the controlled surface roughness Ra of 1.0 or less of at least the first projection located nearest to the top surface, high sliding properties and high resistance to liquid leakage can be simultaneously achieved.
  • Fig. 1 is an exemplary longitudinal cross-sectional view (cross-sectional view in the sliding direction (longitudinal cross-section)) of a base material 1 (gasket base material 1) on which polymer chains are to be immobilized.
  • Fig. 2 is an exemplary longitudinal cross-sectional view of a gasket 2 of the present invention in which polymer chains 21 are immobilized on the surface of the gasket base material 1 shown in Fig. 1.
  • Fig. 3 is an exemplary partial enlarged view (area enclosed by the circle) of a first projection 14a of the gasket 2 shown in Fig. 2 .
  • the gasket 2 can be used in, for example, a syringe that includes a barrel into which liquid is injected, a plunger for pushing the injected liquid out of the barrel, and a gasket attached to the tip of the plunger.
  • the gasket 2 in Fig. 2 is prepared by immobilizing polymer chains on at least a part of the sliding surface of the gasket base material 1 shown in Fig. 1 .
  • the circumference of a top surface 12 on the liquid-contact side and the circumference of a bottom surface 13 to be connected to the tip of a plunger are integrated with a sliding portion 14 (cylindrical portion) extending in the height direction (sliding direction).
  • the outer periphery of the sliding portion 14 includes three annular projections that make sliding contact with the inner periphery of the peripheral cylindrical portion of the barrel; specifically, a first projection 14a at a position nearest to the top surface 12 (first projection 14a nearest to the top surface), a bottom projection 14c at a position farthest from the top surface 12 (bottom projection 14c nearest to the bottom surface), and an intermediate projection 14b at a position between the projections 14a and 14c.
  • the top surface 12 is integrated with the first projection 14a.
  • Figs. 1 and 2 show an embodiment having three annular projections, there may be any number, but at least two, of annular projections.
  • the embodiment has one intermediate projection 14b, any projection between the first projection and the bottom projection corresponds to an intermediate projection, and there may be multiple intermediate projections.
  • the gasket 2 preferably has three or more annular projections.
  • the top surface 12 on the liquid-contact side, the bottom surface 13 to be connected to the tip of a plunger, the first projection 14a, the intermediate projection 14b, the bottom projection 14c, and the sliding portion 14 in the straight cylindrical gasket base material 1 or gasket 2 may each have any shape.
  • the gasket 2 in Fig. 2 or Fig. 3 (the partial enlarged view of the first projection 14a) is prepared by immobilizing polymer chains 21 on at least a part of the surface of the gasket base material 1.
  • the figures show an example in which polymer chains 21 are immobilized on the top surface 12 and the entire sliding portion 14 (cylindrical portion) including annular projections (first projection 14a, intermediate projection 14b, and bottom projection 14c).
  • the first projection 14a provided with polymer chains 21 has a surface roughness Ra of 1.0 or less, preferably 0.8 or less, more preferably 0.6 or less.
  • the lower limit is not particularly critical, and a smaller Ra is better.
  • the surface roughness Ra herein refers to a center-line surface roughness Ra defined in JIS B0601-2001.
  • the first projection 14a in the gasket base material 1 (before the immobilization of polymer chains) preferably has a surface roughness Ra of 1.0 or less, more preferably 0.8 or less, still more preferably 0.6 or less.
  • the lower limit is not particularly critical, and a smaller Ra is better.
  • the surface roughness Ra of the gasket base material 1 or the gasket 2 in which polymer chains 21 are immobilized on the gasket base material 1 can be controlled, for example, by varying the surface roughness of the forming mold, specifically by varying the particle size of the abrasive used in the final finishing step in the production of the mold.
  • the abrasive include abrasive grains made of diamond, alumina, silicon carbide, cubic boron nitride, boron carbide, zirconium oxide, manganese oxide, colloidal silica, or other materials. Suitable examples include those of #46 to #100 defined in JIS R6001-1998.
  • the material of the forming mold may be a known material, such as carbon steel or precipitation hardening stainless steel.
  • the forming mold can be produced by cutting methods, such as by cutting with a cemented carbide tool, coated cemented carbide, sintered cBN, or other tools, followed by polishing and finishing.
  • the gasket of the present invention is prepared by immobilizing polymer chains on at least a part of the surface of a gasket base material.
  • the gasket has a sliding surface provided with multiple annular projections.
  • Any polymer chain can be used, including polymer chains formed by polymerization of conventionally known monomers.
  • the polymer chains may be immobilized by any method, including known methods such as the "grafting from” method in which graft polymerization of monomers is initiated from the surface and the "grafting to (on)” method in which polymer chains are reacted with and immobilized on the surface.
  • Such a gasket of the present invention can be produced, for example, by subjecting a gasket base material having a sliding surface provided with multiple annular projections to a surface modification method as described below.
  • the gasket of the present invention can be produced by immobilizing polymer chains using a surface modification method I that includes: Step 1 of forming polymerization initiation points A on the surface of a gasket base material; and Step 2 of radically polymerizing a monomer starting from the polymerization initiation points A to grow polymer chains.
  • Step 1 includes forming polymerization initiation points A on the surface of a vulcanized rubber or a formed thermoplastic elastomer (gasket base material).
  • the vulcanized rubber or the thermoplastic elastomer may suitably be one containing a carbon atom adjacent to a double bond (i.e., allylic carbon atom).
  • the rubber examples include diene rubbers such as styrene-butadiene rubber, polybutadiene rubber, polyisoprene rubber, natural rubber, and deproteinized natural rubber; butyl rubber and halogenated butyl rubber which have a degree of unsaturation of a few percent of isoprene units; and silicone rubber.
  • diene rubbers such as styrene-butadiene rubber, polybutadiene rubber, polyisoprene rubber, natural rubber, and deproteinized natural rubber
  • butyl rubber and halogenated butyl rubber which have a degree of unsaturation of a few percent of isoprene units
  • silicone rubber silicone rubber.
  • butyl rubber or halogenated butyl rubber it is preferably a rubber crosslinked by triazine because the amount of matter extracted from the vulcanized rubber is reduced.
  • the rubber may contain an acid acceptor. Suitable examples of the acid acceptor include hydrotalcite and magnesium carbonate.
  • sulfur vulcanization is preferably performed.
  • compounding ingredients commonly used in sulfur vulcanization may be added, such as vulcanization accelerators, zinc oxide, fillers, and silane coupling agents.
  • Suitable fillers include carbon black, silica, clay, talc, and calcium carbonate.
  • the vulcanization conditions for the rubber may be appropriately selected.
  • the rubber is preferably vulcanized at a temperature of 150°C or higher, more preferably 170°C or higher, still more preferably 175°C or higher.
  • thermoplastic elastomer examples include polymer compounds that have rubber elasticity at room temperature owing to aggregates of plastic components (hard segments) serving as crosslinking points (e.g., thermoplastic elastomers (TPE) such as styrene-butadienestyrene copolymers); and polymer compounds having rubber elasticity produced by mixing thermoplastic and rubber components and dynamically crosslinking the mixture by a crosslinking agent (e.g., thermoplastic elastomers (TPV) such as polymer alloys containing combinations of styrenic block copolymers or olefinic resins with crosslinked rubber components).
  • TPE thermoplastic elastomers
  • TPV thermoplastic elastomers
  • thermoplastic elastomers include nylon, polyester, polyurethane, polypropylene, fluoroelastomers such as PTEF, and dynamically crosslinked thermoplastic elastomers thereof.
  • dynamically crosslinked thermoplastic elastomers are those produced by dynamically crosslinking halogenated butyl rubber in thermoplastic elastomer.
  • the thermoplastic elastomer is preferably, for example, nylon, polyurethane, polypropylene, styrene-isobutylene-styrene block copolymer (SIBS).
  • the polymerization initiation points A may be formed, for example, by adsorbing a photopolymerization initiator A onto the surface of the gasket base material.
  • a photopolymerization initiator A examples include carbonyl compounds, organic sulfur compounds such as tetraethylthiuram disulfide, persulfides, redox compounds, azo compounds, diazo compounds, halogen compounds, and photoreductive pigments. Carbonyl compounds are preferred among these.
  • the carbonyl compound used as a photopolymerization initiator A is preferably benzophenone or its derivative, and may suitably be a benzophenone compound represented by the following formula: wherein R 1 to R 5 and R 1 ' to R 5 ' are the same as or different from one another and each represent a hydrogen atom, an alkyl group, a halogen (fluorine, chlorine, bromine, or iodine), a hydroxy group, a primary to tertiary amino group, a mercapto group, or a hydrocarbon group optionally containing an oxygen atom, a nitrogen atom, or a sulfur atom; and any adjacent two of R 1 to R 5 and R 1 ' to R 5 ' may be joined to each other to form a cyclic structure together with the carbon atoms to which they are attached.
  • R 1 to R 5 and R 1 ' to R 5 ' are the same as or different from one another and each represent a hydrogen atom, an alkyl group, a
  • benzophenone compound examples include benzophenone, xanthone, 9-fluorenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone.
  • benzophenone, xanthone, and 9-fluorenone are particularly preferred because they allow polymer brushes to be well formed.
  • benzophenone compound examples include fluorobenzophenone compounds, such as 2,3,4,5,6-pentafluorobenzophenone and decafluorobenzophenone respectively represented by the following formulas.
  • Thioxanthone compounds can also be suitably used as the photopolymerization initiator A because they provide a high polymerization rate and also can readily be adsorbed onto and/or reacted with rubber or the like.
  • compounds represented by the following formula can be suitably used.
  • R 11 to R 14 and R 11 ' to R 14 ' are the same as or different from one another and each represent a hydrogen atom, a halogen atom, an alkyl group, a cyclic alkyl group, an aryl group, an alkenyl group, an alkoxy group, or an aryloxy group.
  • thioxanthone compounds represented by the above formula include thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,3-diethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-methoxythioxanthone, 1-chloro-4-propoxythioxanthone, 2-cyclohexylthioxanthone, 4-cyclohexylthioxanthone, 2-vinylthioxanthone, 2,4-divinylthioxanthone, 2,4-diphenylthioxanthone, 2-butenyl-4-phenylthioxanthone, 2-methoxythioxanthone, and 2-p-octyloxyphenyl-4-ethylthioxanthone. Preferred among these are those which are substituted at one or two, particularly
  • the photopolymerization initiator A such as a benzophenone or thioxanthone compound can be adsorbed onto the surface of the gasket base material by known methods.
  • a benzophenone or thioxanthone compound the benzophenone or thioxanthone compound is dissolved in an organic solvent to prepare a solution, and a surface portion of the gasket base material to be modified is treated with this solution so that the compound is adsorbed onto the surface, optionally followed by evaporating off the organic solvent by drying, to form polymerization initiation points.
  • the surface may be treated by any method that allows the solution of the benzophenone or thioxanthone compound to be brought into contact with the surface of the gasket base material.
  • Suitable examples of the surface treatment method include application or spraying of the benzophenone or thioxanthone compound solution; and immersion into the solution. In the case where only a part of the surface needs to be modified, it is sufficient to adsorb the photopolymerization initiator A only onto the desired part of the surface. In this case, for example, application or spraying of the solution is suitable.
  • the solvent include methanol, ethanol, acetone, benzene, toluene, methyl ethyl ketone, ethyl acetate, and THF. Acetone is preferred because it does not swell the gasket base material and it rapidly dries and evaporates.
  • the surface of the gasket base material is preferably further irradiated with light so that the polymerization initiator A is chemically bonded to the surface.
  • the benzophenone or thioxanthone compound may be immobilized on the surface by irradiation with ultraviolet light having a wavelength of 300 to 450 nm, preferably 300 to 400 nm, more preferably 350 to 400 nm.
  • the rubber preferably contains a butadiene or isoprene unit that contains an allylic hydrogen atom.
  • the polymerization initiation points A are preferably formed by treating the surface of the gasket base material with the photopolymerization initiator A so that the photopolymerization initiator A is adsorbed onto the surface, and then irradiating the treated surface with LED light having a wavelength of 300 to 450 nm.
  • the treated surface is further irradiated with LED light having a wavelength of 300 to 450 nm so that the adsorbed photopolymerization initiator A is chemically bonded to the surface.
  • light having a wavelength of less than 300 nm may break and damage the molecules in the gasket base material
  • light having a wavelength of 300 nm or more is preferably used.
  • Light having a wavelength of 355 nm or more is more preferred in that such light causes only very small damage to the gasket base material.
  • light having a wavelength of more than 450 nm is less likely to activate the polymerization initiator and thus less likely to allow the polymerization reaction to proceed, light having a wavelength of 450 nm or less is preferred.
  • Light having a wavelength of 400 nm or less is more preferred for greater activation of the polymerization initiator.
  • LED light having a wavelength of 355 to 380 nm is particularly suitable.
  • LED light is suitable in that the wavelength range of LED light is narrow so that no wavelengths other than the center wavelength are emitted
  • mercury lamps or other light sources can also produce similar effects to those of LED light by using a filter to block light with wavelengths less than 300 nm.
  • Step 2 includes radically polymerizing a monomer starting from the polymerization initiation points A to grow polymer chains.
  • Non-limiting examples of the monomer include hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate and hydroxybutyl (meth)acrylate, (meth)acrylic acid, dimethyl (meth)acrylamide, diethyl (meth)acrylamide, isopropyl (meth)acrylamide, hydroxyethyl (meth)acrylamide, methoxymethyl (meth)acrylamide, (meth)acrylamide, methoxymethyl (meth)acrylate, and (meth)acrylonitrile. These monomers may be used alone, or two or more of these may be used in combination.
  • the monomer used in Step 2 is preferably (meth)acrylic acid, a hydroxyalkyl (meth)acrylate, dimethyl (meth)acrylamide, diethyl (meth)acrylamide, isopropyl (meth)acrylamide, hydroxyethyl (meth)acrylamide, methoxymethyl (meth)acrylamide, (meth)acrylamide, or methoxymethyl (meth)acrylate, more preferably (meth)acrylic acid or (meth)acrylamide, still more preferably acrylic acid or acrylamide, among others.
  • the monomer may suitably be a fluorine-containing monomer.
  • fluorine-containing monomer examples include fluorine-containing (meth)acrylic-modified organosilicon compounds and cyclic siloxanes.
  • the fluorine-containing monomer preferably contains a perfluoropolyether group in order to better achieve the effects of the present invention.
  • the fluorine-containing monomer may suitably be, for example, a fluorine-containing (meth)acrylic-modified organosilicon compound produced by an addition reaction of (B) an unsaturated monocarboxylic acid containing a (meth)acrylic group with (A) a fluorine-containing epoxy-modified organosilicon compound represented by the following formula (1) : wherein Rf 11 represents a monovalent or divalent group having a molecular weight of 100 to 40,000 and containing a fluoroalkyl structure or a fluoropolyether structure; Q 11 represents an (a+b)-valent linking group containing at least (a+b) silicon atoms and having a siloxane structure, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more thereof, and Q 11 may form a cyclic structure; Q 12 represents a C1-20 divalent hydrocarbon group which may form a cycl
  • Q 11 in formula (1) include groups having the structures represented by the following formulas.
  • a and b are as defined above and are each preferably an integer of 1 to 4. Moreover, (a+b) is preferably an integer of 3 to 5.
  • the unit repeated a times and the unit repeated b times are randomly arranged.
  • the bond represented by the broken line in each of the units repeated a times and b times is attached to Rf 11 or the group represented by the following formula: wherein Q 12 and R 11 to R 13 are as defined above.
  • the divalent hydrocarbon group for Q 12 in formula (1) preferably has 2 to 15 carbon atoms.
  • Specific examples of the structure of Q 12 include -CH 2 CH 2 -, -CH 2 CH(CH 3 )-, and - CH 2 CH 2 CH 2 OCH 2 -.
  • the monovalent hydrocarbon group for R 11 to R 13 preferably has 1 to 8 carbon atoms.
  • R 11 to R 13 include a hydrogen atom, alkyl groups such as methyl, ethyl, and propyl groups, and cycloalkyl groups such as cyclopentyl and cyclohexyl groups.
  • Examples of the group containing a combination of R 11 to R 13 and Q 12 represented by the above formula include the following groups.
  • Rf 11 in formula (1) preferably has a molecular weight of 500 to 20,000.
  • Rf 11 may suitably contain 1 to 500, preferably 2 to 400, more preferably 4 to 200 repeating units of the formula: -C i F 2i O- where i in each unit independently represents an integer of 1 to 6.
  • the term "molecular weight” refers to a number average molecular weight calculated from the ratio between the chain end structure and the backbone structure as determined by 1 H-NMR and 19 F-NMR.
  • Rf 11 in formula (1) examples include groups represented by the following formula (3): wherein Rf' 11 represents a divalent perfluoropolyether group having a molecular weight of 300 to 30,000 which may be internally branched; Q 13 represents a divalent organic group which may contain an oxygen atom, a nitrogen atom, a fluorine atom, or a silicon atom, and may contain a cyclic structure or an unsaturated bond; Q f 11 represents Q 13 or a fluorine atom; T represents a linking group represented by the following formula (4): wherein R 11 to R 13 , Q 12 , a, and b are as defined in formula (1), and Q 14 represents an (a+b)-valent linking group containing at least (a+b) silicon atoms and having a siloxane structure, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more thereof; and v represents an integer of 0 to
  • Rf' 11 in formula (3) preferably has a molecular weight of 500 to 20,000.
  • Rf' 11 include divalent perfluoropolyether groups represented by the following formulas: wherein each Y independently represents a fluorine atom or CF 3 group; r represents an integer of 2 to 6; m and n each represent an integer of 0 to 200, preferably 0 to 100, provided that (m+n) is an integer of 2 to 200, preferably 3 to 150; s represents an integer of 0 to 6; and the repeating units may be randomly linked, and -C j F 2j (OCF 2 CF 2 CF 2 ) k OC j F 2j - wherein j represents an integer of 1 to 3, and k represents an integer of 1 to 200, preferably 1 to 60.
  • Examples of Q 13 in formula (3) include the following groups: -CH 2 CH 2 - -CH 2 CH 2 CH 2 - -CHpOCH 2 CH 2 CH 2 - wherein Ph represents a phenyl group.
  • Rf 11 when Rf 11 is a monovalent group, a is preferably an integer of 1 to 3; b is preferably an integer of 1 to 6; and (a+b) is preferably an integer of 3 to 6.
  • Rf 11 in formula (1) include the following groups: wherein m, n, r, and s are as defined above.
  • fluorine-containing epoxy-modified organosilicon compound (A) include the following compounds: wherein j, m, and n are as defined above, and b' is an integer of 1 to 8.
  • fluorine-containing epoxy-modified organosilicon compounds may be used alone, or two or more of these may be used in combination.
  • the unsaturated monocarboxylic acid (B) containing a (meth)acrylic group may suitably be acrylic acid or methacrylic acid and may also be one in which a part of the hydrogen atoms is halogenated with a halogen atom (e.g. chlorine, fluorine), such as 2-chloroacrylic acid, 2-(trifluoromethyl)acrylic acid, or 2,3,3-trifluoroacrylic acid.
  • a halogen atom e.g. chlorine, fluorine
  • the carboxylic acids may optionally be protected by an allyl group, a silyl group, or other groups.
  • the unsaturated monocarboxylic acids may be used alone, or two or more of these may be used in combination.
  • the fluorine-containing (meth)acrylic-modified organosilicon compound may be produced by reacting the epoxy group of the fluorine-containing epoxy-modified organosilicon compound (A) with the carboxyl group of the unsaturated monocarboxylic acid (B) containing a (meth)acrylic group by a known method.
  • Specific examples of the fluorine-containing (meth)acrylic-modified organosilicon compound include the following compounds: wherein j, m, n, and b' are as defined above.
  • the fluorine-containing monomer may suitably be a mixture of a fluorine-containing epoxy-modified organosilicon compound as specifically exemplified above and a fluorine-containing (meth)acrylic-modified organosilicon compound as specifically exemplified above. It is particularly preferably a mixture of a fluorine-containing epoxy-modified organosilicon compound and a fluorine-containing (meth)acrylic-modified organosilicon compound as represented by the formulas below: wherein (b' 1 +b' 2 ) is 2 to 6.5, and Rf' 12 is a group represented by the following formula: wherein n 1 is 2 to 100. In this case, the effects of the present invention can be better achieved.
  • the fluorine-containing monomer may also be a polyfunctional (meth)acrylate compound containing, per molecule, three or more fluorine atoms and three or more silicon atoms and having a cyclic siloxane represented by the following formula: (Rf 21 R 21 SiO)(R A R 21 SiO) h wherein R 21 represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a phenyl group; Rf 21 represents a fluorine-containing organic group; R A represents a (meth)acrylic group-containing organic group; and h satisfies h ⁇ 2.
  • Rf 21 in the polyfunctional (meth)acrylate compound may be a group represented by C t F 2t+1 (CH 2 ) u - where t represents an integer of 1 to 8, and u represents an integer of 2 to 10, or may be a perfluoropolyether-substituted alkyl group.
  • Specific examples include CF 3 C 2 H 4 -, C 4 F 9 C 2 H 4 -,C 4 F 9 C 3 H 6 -, C 8 F 17 C 2 H 4 -, C 8 F 17 C 3 H 6 -, C 3 F 7 C(CF 3 ) 2 C 3 H 6 -, C 3 F 7 OC(CF 3 )FCF 2 OCF 2 CF 2 C 3 H 6 -, C 3 F 7 OC(CF 3 )FCF 2 OC(CF 3 )FC 3 H 6 -, and CF 3 CF 2 CF 2 OC(CF 3 )FCF 2 OC(CF 3 )FCONHC 3 H 6 -.
  • R A is preferably bonded to the silicon atom by a Si-O-C bond.
  • the symbol h preferably satisfies 3 ⁇ h ⁇ 5.
  • the polyfunctional (meth)acrylate compound contains, per molecule, three or more fluorine atoms and three or more silicon atoms, and preferably contains, per molecule, 3 to 17 fluorine atoms and 3 to 8 silicon atoms.
  • polyfunctional (meth)acrylate compound examples include compounds represented by the following formulas.
  • the fluorine-containing monomer is also preferably characterized by an infrared absorption spectrum with absorption peaks at about 1,045 cm -1 , about 1,180 cm -1 , about 806 cm -1 , about 1,720 cm -1 , about 1,532 cm -1 , and about 3,350 cm -1 .
  • it may suitably be characterized by an infrared absorption spectrum with strong absorption peaks at about 1,045 cm -1 and about 1,180 cm -1 , absorption peaks at about 806 cm -1 and about 1,720 cm -1 , a weak absorption peak at about 1,532 cm -1 , and a broad weak absorption peak at about 3,350 cm -1 .
  • Such a monomer can be used to form polymer chains having better properties such as sliding properties.
  • the fluorine-containing monomer is preferably characterized by a 13 C-NMR spectrum in chloroform-d (deuterated chloroform) having signals at chemical shifts of about 13.01, 14.63, 23.04, 40.13, 50.65, 63.54, 68.97, 73.76, 76.74, 77.06, 77.38, 113.21, 114.11, 116.96, 117.72, 118.47, 128.06, 131.38, 156.46, and 166.02 ppm.
  • the fluorine-containing monomer is also preferably characterized by a 1 H-NMR spectrum in chloroform-d (deuterated chloroform) having signals at chemical shifts of about 3.40, 3.41, 3.49, 3.60, 5.26, 5.58, 6.12, 6.14, 6.40, 6.42, and 6.46 ppm.
  • the monomer may be radically polymerized as follows.
  • a solution of the monomer or the liquid monomer is applied (sprayed) to the surface of the gasket base material to which a benzophenone or thioxanthone compound or the like is adsorbed or covalently bonded.
  • the gasket base material is immersed in a solution of the monomer or the liquid monomer. Then, the gasket base material is irradiated with light, such as ultraviolet light, to allow the radical polymerization (photoradical polymerization) to proceed, whereby polymer chains can be grown on the surface of the gasket base material.
  • light such as ultraviolet light
  • the surface may be covered with a transparent cover of glass, PET, polycarbonate, or other materials, followed by irradiating the covered surface with light, such as ultraviolet light, to allow the radical polymerization (photoradical polymerization) to proceed, whereby polymer chains can be grown on the surface of the gasket base material.
  • light such as ultraviolet light
  • the amount of the radically polymerizable monomer may be selected appropriately depending on, for example, the length of polymer chains to be formed, or the properties to be provided by the chains.
  • the solvent for application may be conventionally known materials or methods.
  • the solution of the radically polymerizable monomer may be an aqueous solution, or a solution in an organic solvent that does not dissolve the photopolymerization initiator used (e.g. benzophenone or thioxanthone compound).
  • a solution of the radically polymerizable monomer or the liquid radically polymerizable monomer may contain a known polymerization inhibitor such as 4-methylphenol.
  • the radical polymerization of the monomer is allowed to proceed by light irradiation after the application of a solution of the monomer or the liquid monomer or after the immersion in a solution of the monomer or the liquid monomer.
  • UV light sources with an emission wavelength mainly in the ultraviolet region, such as high-pressure mercury lamps, metal halide lamps, and LED lamps, can be suitably used.
  • the light dose may be appropriately selected in view of polymerization time and uniform reaction progress.
  • oxygen is preferably removed from the reaction vessel and the reaction solution during or before the light irradiation. For this purpose, appropriate operations may be performed.
  • an inert gas such as nitrogen gas or argon gas is inserted into the reaction vessel and the reaction solution to discharge active gases such as oxygen from the reaction system and thereby replace the atmosphere in the reaction system with the inert gas.
  • the reaction vessel is evacuated to remove oxygen.
  • a measure may appropriately be taken; for example, an UV light source is placed such that an air layer (oxygen content: 15% or higher) does not exist between the reaction vessel made of glass, plastic, or other materials and the reaction solution or the gasket base material.
  • the ultraviolet light preferably has a wavelength of 300 to 450 nm, more preferably 300 to 400 nm.
  • the light source may be, for example, a high-pressure mercury lamp, an LED with a center wavelength of 365 nm, or an LED with a center wavelength of 375 nm.
  • irradiation with LED light having a wavelength of 300 to 450 nm, more preferably 355 to 380 nm.
  • LEDs or other light sources having a center wavelength of 365 nm, which is close to the excitation wavelength (366 nm) of benzophenone, are particularly preferred in view of efficiency.
  • the surface modification method I may include (i) Step 3 of extending the polymer chains grown in Step 2 with the same type or a different type of polymer chain, or (ii) Step 3' of attaching a silane compound to the surfaces of the polymer chains grown in Step 2, followed by reaction with a perfluoroether group-containing silane compound to grow functional polymer chains.
  • Step 3 is not particularly limited as long as it involves further extending the polymer chains.
  • Step 3 may include Step 3-1 of forming polymerization initiation points B on the surfaces of the polymer chains grown in Step 2, and Step 3-2 of radically polymerizing a monomer starting from the polymerization initiation points B to grow polymer chains.
  • Step 3-1 the formation of polymerization initiation points B may be carried out by the same techniques as described in Step 1, such as by additionally adsorbing a photopolymerization initiator B onto the surfaces of the formed polymer chains, optionally followed by chemically bonding the photopolymerization initiator B to the surfaces.
  • the photopolymerization initiator B may be as described for the photopolymerization initiator A.
  • Step 3-2 a monomer is radically polymerized starting from the polymerization initiation points B to grow polymer chains.
  • the monomer used in Step 3-2 may be as described for the monomer used in Step 2.
  • the monomer is preferably (meth)acrylonitrile or a fluorine-containing monomer, more preferably a fluorine-containing monomer, because they provide excellent resistance to liquid leakage and excellent sliding properties.
  • the monomer may be radically polymerized as described for the radical polymerization in Step 2.
  • Step 3 the cycle of Steps 3-1 and 3-2 may further be repeated.
  • the polymer chains that have been chain extended in Steps 3-1 and 3-2 are extended with additional polymer chains.
  • Step 3' on the other hand, a silane compound is attached to the surfaces of the polymer chains formed in Step 2, and then reacted with a perfluoroether group-containing silane compound to grow functional polymer chains (functional regions).
  • the silane compound is not particularly limited, and suitable examples include alkoxysilanes and modified alkoxysilanes. These compounds may be used alone, or two or more of these may be used in combination. Among these, alkoxysilanes are more preferred in order to better achieve the effects of the present invention.
  • alkoxysilanes include: monoalkoxysilanes such as trimethylmethoxysilane, triethylethoxysilane, tripropylpropoxysilane, and tributylbutoxysilane; dialkoxysilanes such as dimethyldimethoxysilane, diethyldiethoxysilane, dipropyldipropoxysilane, and dibutyldibutoxysilane; trialkoxysilanes such as methyltrimethoxysilane, ethyltriethoxysilane, propyltripropoxysilane, and butyltributoxysilane; and tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, dibutoxydiethoxysilane, butoxytriethoxysilane, and ethoxytriethoxy
  • tetraalkoxysilanes are preferred among these, with tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dibutoxydiethoxysilane, butoxytriethoxysilane, and ethoxytributoxysilane being more preferred.
  • modified alkoxysilane refers to an alkoxysilane having a substituent such as an amino, carboxyl, hydroxy, or epoxy group, and preferably contains at least one substituent selected from the group consisting of alkyl, amino, carboxyl, hydroxy, and epoxy groups.
  • the alkoxysilane or modified alkoxysilane preferably has 4 to 22 carbon atoms, more preferably 4 to 16 carbon atoms.
  • the alkoxysilane or modified alkoxysilane preferably contains at least one selected from the group consisting of methoxy, ethoxy, propoxy, and butoxy groups, more preferably ethoxy and/or butoxy group(s), still more preferably ethoxy and butoxy groups.
  • the silane compound may be attached to the surfaces of the polymer chains by any method, and conventionally known methods may appropriately be used, such as bringing the silane compound into contact with the object to be modified on which polymer chains are formed.
  • the perfluoroether group-containing silane compound may be any silane compound containing a perfluoroether group.
  • it may suitably be a compound represented by the following formula (A) or (B): wherein Rf 1 represents a perfluoroalkyl group; Z represents fluorine or a trifluoromethyl group; a, b, c, d, and e are the same as or different from one another and each represent an integer of 0 or 1 or more, provided that (a+b+c+d+e) is 1 or more and the order of the repeating units parenthesized by subscripts a, b, c, d, and e occurring in the formula is not limited to that shown; Y represents hydrogen or a C1-C4 alkyl group; X 1 represents hydrogen, bromine, or iodine; R 1 represents a hydroxy group or a hydrolyzable substituent such as a C1-C4 alkoxy group; R 2 represents hydrogen or a monovalent hydrocarbon
  • Rf 1 in formula (A) may be any perfluoroalkyl group that can be present in a common organic-containing fluoropolymer, and examples include linear or branched C1-C16 groups. In particular, CF 3 -, C 2 F 5 -, and C 3 F 7 - are preferred.
  • each of a, b, c, d, and e represents the number of repeating units in the perfluoropolyether chain which forms the backbone of the fluorine-containing silane compound, and is independently preferably 0 to 200, more preferably 0 to 50. Moreover, (a+b+c+d+e), i.e. the sum of a to e, is preferably 1 to 100.
  • the order of the repeating units parenthesized by subscripts a, b, c, d, and e occurring in formula (A) is not limited to the order shown, and the repeating units may be joined in any order.
  • Examples of the C1-C4 alkyl group represented by Y in formula (A) include methyl, ethyl, propyl, and butyl groups, and the alkyl group may be linear or branched.
  • X 1 is bromine or iodine, the fluorine-containing silane compound easily forms a chemical bond.
  • the monovalent hydrocarbon group represented by R 2 is not particularly limited, and preferred examples include methyl, ethyl, propyl, and butyl groups. The hydrocarbon group may be linear or branched.
  • 1 represents the number of carbon atoms of the alkylene group between the carbon in the perfluoropolyether chain and the silicon attached thereto and is preferably 0; and m represents the number of substituents R 1 bonded to the silicon to which R 2 is bonded through a bond not attached to R 1 .
  • the upper limit of n is not particularly critical and is preferably an integer of 1 to 10.
  • the group represented by Rf 2 is preferably, but not limited to, such that when each s is 0, the ends of the Rf 2 group bonded to oxygen atoms in formula (B) are not oxygen atoms.
  • k in Rf 2 is preferably an integer of 1 to 4.
  • Rf 2 Specific examples of the group represented by Rf 2 include -CF 2 CF 2 O(CF 2 CF 2 CF 2O ) j CF 2 CF 2 - in which j represents an integer of 1 or more, preferably an integer of 1 to 50, more preferably 10 to 40; and - CF 2 (OC 2 F 4 ) p -(OCF 2 ) q - in which p and q each represent an integer of 1 or more, preferably an integer of 1 to 50, more preferably 10 to 40, and the sum of p and q is an integer of 10 to 100, preferably 20 to 90, more preferably 40 to 80, and the repeating units (OC 2 F 4 ) and (OCF 2 ) are randomly arranged.
  • R 3 in formula (B) is preferably a C1-C30 monovalent hydrocarbon group, and examples include: alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; aryl groups such as phenyl, tolyl, and xylyl groups; aralkyl groups such as benzyl and phenethyl groups; and alkenyl groups such as vinyl, allyl, butenyl, pentenyl, and hexenyl groups. Preferred among these is a methyl group.
  • Examples of the hydrolyzable group represented by X 2 in formula (B) include: alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups; alkoxyalkoxy groups such as methoxymethoxy, methoxyethoxy, and ethoxyethoxy groups; alkenyloxy groups such as allyloxy and isopropenoxy groups; acyloxy groups such as acetoxy, propionyloxy, butylcarbonyloxy, and benzoyloxy groups; ketoxime groups such as dimethylketoxime, methylethylketoxime, diethylketoxime, cyclopennoxime, and cyclohexanoxime groups; amino groups such as N-methylamino, N-ethylamino, N-propylamino, N-butylamino, N,N-dimethylamino, N,N-diethylamino, and N-cyclohexylamino groups; amide groups such as N
  • s is preferably 1, and t is preferably 3.
  • h and i are each preferably 3.
  • the perfluoroether group-containing silane compound preferably has an average molecular weight in the range of 1,000 to 10,000.
  • the average molecular weight can be determined by gel permeation chromatography (GPC) calibrated with polystyrene standards.
  • Examples of commercial products of the perfluoroether group-containing silane compound include OPTOOL DSX and OPTOOL DSX-E (Daikin Industries, Ltd.), KY-108 and KY-164 (Shin-Etsu Chemical Co., Ltd.), Fluorolink S10 (Solvay Specialty Polymers Japan K.K.), Novec 2702 and Novec 1720 (3M Japan Limited), and FLUOROSURF series such as FLUOROSURF FG-5080SH (Fluoro Technology).
  • the reaction with the perfluoroether group-containing silane compound may be carried out by any method, and conventionally known methods may appropriately be used, such as bringing a solution of the perfluoroether group-containing silane compound into contact with the object to be modified to which the silane compound is attached.
  • the solution of the perfluoroether group-containing silane compound may be prepared by using a known solvent that can dissolve the compound (e.g. water, perfluorohexane, acidic water, methanol, ethanol, a mixture of water and methanol or ethanol, or C 4 F 9 OC 2 H 5 ), followed by appropriately adjusting the concentration.
  • the contact between the solution and the object may be made by any method that brings them into contact with each other, such as application, spraying, or immersion.
  • the contact e.g. immersion
  • the humidity is more preferably 60% or higher, still more preferably 80% or higher.
  • the upper limit of the humidity is not particularly critical but is preferably, for example, 100% or lower.
  • the holding time and temperature may be appropriately selected and are preferably, for example, 0.5 to 60 hours and 20°C to 110°C, respectively.
  • the gasket of the present invention may also be produced by immobilizing polymer chains using a surface modification method II that includes Step I of radically polymerizing a monomer in the presence of a photopolymerization initiator A on the surface of a gasket base material to grow polymer chains.
  • Step I may be carried out by bringing a photopolymerization initiator A and a monomer into contact with the surface of a gasket base material, followed by irradiation with LED light having a wavelength of 300 to 450 nm to form polymerization initiation points A from the photopolymerization initiator A while radically polymerizing the monomer starting from the polymerization initiation points A to grow polymer chains.
  • the surface modification method including Step I may include (i) Step II of extending the polymer chains grown in Step I with the same type or a different type of polymer chain; or (ii) Step II' of attaching a silane compound to the surfaces of the polymer chains grown in Step I, followed by reaction with a perfluoroether group-containing silane compound to grow functional polymer chains.
  • Step II may be carried out by bringing a photopolymerization initiator B and a monomer into contact with the surfaces of the polymer chains formed in Step I, followed by irradiation with LED light having a wavelength of 300 to 450 nm to form polymerization initiation points B from the photopolymerization initiator B while radically polymerizing the monomer starting from the polymerization initiation points B to grow polymer chains.
  • the extension process may be repeated in Step II. In this case, the polymer chains that have been chain extended are further extended.
  • the monomers may be radically polymerized as follows.
  • a solution of the monomer or the liquid monomer, which contains the photopolymerization initiator A or B e.g. benzophenone or thioxanthone compound
  • the gasket base material or the gasket base material on which polymer chains are formed in Step I is immersed in a solution of the monomer or the liquid monomer, which contains the photopolymerization initiator A or B.
  • the gasket base material is irradiated with light, such as ultraviolet light, to allow the radical polymerization (photoradical polymerization) to proceed, whereby polymer chains can be grown or extended on the surface of the gasket base material.
  • light such as ultraviolet light
  • the surface may be covered with a transparent cover of glass, PET, polycarbonate, or other materials, followed by irradiating the covered surface with light such as ultraviolet light, as described above.
  • a reducing agent or an antioxidant may be added.
  • the solvent for application may beying), the method for application (spraying), the method for immersion, the conditions for irradiation, and other conditions may be materials or methods as described above.
  • Step II' on the other hand, a silane compound is attached to the surfaces of the polymer chains grown in Step I, and then reacted with a perfluoroether group-containing silane compound to grow functional polymer chains (functional regions).
  • Step II' may be carried out as described in Step 3'.
  • the polymer chains finally formed by the surface modification method preferably have a degree of polymerization of 500 to 50,000, more preferably 1,000 to 25,000.
  • the total length of the finally formed polymer chain is preferably 500 to 5,000 nm, more preferably 700 to 2,500 nm. If the total length is shorter than 500 nm, good sliding properties tend not to be obtained. If the total length is longer than 5,000 nm, a further improvement in sliding properties cannot be expected while the cost of raw materials tends to increase due to the use of the expensive monomer. In addition, surface patterns generated by the surface treatment tend to be visible to the naked eyes, thereby spoiling the appearance or deteriorating sealing properties.
  • two or more types of monomers may simultaneously be radically polymerized starting from the polymerization initiation points A or B.
  • multiple types of polymer chains may be grown on the surface of the gasket base material.
  • the polymer chains may be crosslinked to one another.
  • the polymer chains may be crosslinked to one another by ionic crosslinking, crosslinking by a hydrophilic group containing an oxygen atom, or crosslinking by a halogen group such as iodine.
  • Crosslinking by UV irradiation or electron beam irradiation may also be employed.
  • the surface of the gasket base material may be at least partially or entirely provided with polymer chains.
  • at least the sliding surface of the gasket base material is modified.
  • Gasket base materials (isoprene unit-containing chlorobutyl rubber with a degree of unsaturation of 1% to 2%) having the shape ( Fig. 1 , three annular projections (first projection, intermediate projection, and bottom projection)) and surface roughnesses Ra indicated in Table 1 were prepared by crosslinking by triazine (vulcanization at 180°C for 10 minutes) using molds having the respective surface roughnesses.
  • the surface roughness Ra of the surface of each gasket base material was controlled by appropriately varying the surface roughness of the mold (or varying the particle size of the abrasive used in the final finishing step in the production of the mold).
  • the gasket base material indicated in Table 1 was immersed in a 3 wt% solution of benzophenone in acetone for 5 minutes so that benzophenone was adsorbed onto the surface of the gasket base material, followed by drying.
  • the dried gasket base material was immersed in a 2.5 M acrylamide aqueous solution in a glass reaction vessel and subsequently irradiated with LED-UV light having a wavelength of 365 nm for 200 minutes to cause radical polymerization, whereby polymer chains were grown on the rubber surface. Accordingly, a desired gasket ( Fig. 2 ) was prepared.
  • the gasket base material indicated in Table 1 was immersed in a 3 wt% solution of benzophenone in acetone for 5 minutes so that benzophenone was adsorbed onto the surface of the gasket base material, followed by drying.
  • the dried gasket base material was immersed in a 2.5 M acrylamide aqueous solution in a glass reaction vessel and subsequently irradiated with LED-UV light having a wavelength of 365 nm for 150 minutes to cause radical polymerization, whereby polymer chains were grown on the rubber surface. Accordingly, a desired gasket ( Fig. 2 ) was prepared.
  • the gasket base material indicated in Table 1 was immersed in a 3 wt% solution of benzophenone in acetone so that benzophenone was adsorbed onto the surface of the gasket base material, followed by drying.
  • the gasket base material indicated in Table 1 was immersed in a 3 wt% solution of benzophenone in acetone so that benzophenone was adsorbed onto the surface of the gasket base material, followed by drying.
  • the gasket base material indicated in Table 1 was immersed in a 2.5 M aqueous mixture of acrylic acid and acrylamide (25:75) (prepared by dissolving 4.5 g of acrylic acid and 13.4 g of acrylamide in 100 mL of water and then dissolving 2 mg of benzophenone in the solution) in a glass reaction vessel, followed by irradiation with LED-UV light having a wavelength of 365 nm for 120 minutes to cause radical polymerization, whereby polymer chains were grown on the rubber surface. Accordingly, a desired gasket ( Fig. 2 ) was prepared.
  • the gasket base material indicated in Table 1 was immersed in a 3 wt% solution of benzophenone in acetone so that benzophenone was adsorbed onto the surface of the gasket base material, followed by drying.
  • the dried vulcanized rubber gasket was again immersed in a 3 wt% solution of benzophenone in acetone for 5 minutes so that benzophenone was adsorbed onto the surfaces of the polymer chains, followed by drying.
  • a fluorine-containing monomer liquid (a 20 wt% dilution in ethanol of KY-1203 available from Shin-Etsu Chemical Co., Ltd. (a mixture of a fluorine-containing epoxy-modified organosilicon compound and a fluorine-containing (meth)acrylic-modified organosilicon compound as represented by the formulas below)) was applied to the surface of the dried vulcanized rubber gasket, followed by irradiation with LED-UV light having a wavelength of 365 nm for 10 minutes to cause radical polymerization, whereby the polymer chains were extended. Accordingly, a desired gasket ( Fig. 2 ) was prepared.
  • (b' 1 +b '2 ) is 2 to 6.5
  • Rf' 12 is the following group: wherein n 1 is 2 to 100.
  • the gasket base material indicated in Table 1 was immersed in a 3 wt% solution of benzophenone in acetone so that benzophenone was adsorbed onto the surface of the gasket base material, followed by drying.
  • the dried vulcanized rubber gasket was immersed in a silane compound (Primer coat PC-3B available from Fluoro Technology, a butoxy/ethoxy tetraalkoxysilane represented by the above formula), taken out, and dried.
  • a silane compound (Primer coat PC-3B available from Fluoro Technology, a butoxy/ethoxy tetraalkoxysilane represented by the above formula), taken out, and dried.
  • the dried vulcanized rubber gasket was immersed in a 2% solution of a perfluoroether group-containing silane compound (OPTOOL DSX-E available from Daikin Industries, Ltd., a compound of formula (A)) in C 4 F 9 OC 2 H 5 (Novec HFE-7200 available from 3M) and taken out of the solution.
  • the resulting gasket was left at a humidity of 90% for 24 hours to cause a reaction. Thereafter, the gasket was washed with acetone and dried. Accordingly, a desired gasket ( Fig. 2 ) was prepared.
  • the gasket base material indicated in Table 1 was immersed in a 3 wt% solution of benzophenone in acetone so that benzophenone was adsorbed onto the surface of the gasket base material, followed by drying.
  • the dried vulcanized rubber gasket was immersed in a silane compound (Primer coat PC-3B available from Fluoro Technology, a butoxy/ethoxy tetraalkoxysilane represented by the above formula), taken out, and dried.
  • a silane compound (Primer coat PC-3B available from Fluoro Technology, a butoxy/ethoxy tetraalkoxysilane represented by the above formula), taken out, and dried.
  • the dried vulcanized rubber gasket was immersed in a 2% solution of a perfluoroether group-containing silane compound (OPTOOL DSX-E available from Daikin Industries, Ltd., a compound of formula (A)) in C 4 F 9 OC 2 H 5 (Novec HFE-7200 available from 3M) and taken out of the solution.
  • the resulting gasket was left at a humidity of 90% for 24 hours to cause a reaction. Thereafter, the gasket was washed with acetone and dried. Accordingly, a desired gasket ( Fig. 2 ) was prepared.
  • the gasket base material indicated in Table 1 was immersed in a 3 wt% solution of benzophenone in acetone so that benzophenone was adsorbed onto the surface of the gasket base material, followed by drying.
  • the dried vulcanized rubber gasket was immersed in a silane compound (Primer coat PC-3B available from Fluoro Technology, a butoxy/ethoxy tetraalkoxysilane represented by the above formula), taken out, and dried.
  • a silane compound (Primer coat PC-3B available from Fluoro Technology, a butoxy/ethoxy tetraalkoxysilane represented by the above formula), taken out, and dried.
  • the dried vulcanized rubber gasket was immersed in a 2% solution of a perfluoroether group-containing silane compound (OPTOOL DSX-E available from Daikin Industries, Ltd., a compound of formula (A)) in C 4 F 9 OC 2 H 5 (Novec HFE-7200 available from 3M) and taken out of the solution.
  • the resulting gasket was left at a humidity of 90% for 24 hours to cause a reaction. Thereafter, the gasket was washed with acetone and dried. Accordingly, a desired gasket ( Fig. 2 ) was prepared.
  • a gasket ( Fig. 2 ) was prepared as in Example 7, except that the gasket base material indicated in Table 1 was used.
  • the gasket base material indicated in Table 1 was used as it was.
  • the gasket base material indicated in Table 1 was used as it was.
  • the gasket base material indicated in Table 1 was immersed in a 3 wt% solution of benzophenone in acetone so that benzophenone was adsorbed onto the surface of the gasket base material, followed by drying.
  • the dried gasket base material was immersed in a 2.5 M acrylamide aqueous solution in a glass reaction vessel and subsequently irradiated with LED-UV light having a wavelength of 365 nm for 240 minutes to cause radical polymerization, whereby polymer chains were grown on the rubber surface. Accordingly, a desired gasket was prepared.
  • the gasket base material indicated in Table 1 was immersed in a 3 wt% solution of benzophenone in acetone for 5 minutes so that benzophenone was adsorbed onto the surface of the gasket base material, followed by drying.
  • the dried gasket base material was immersed in a 2.5 M acrylamide aqueous solution in a glass reaction vessel and subsequently irradiated with LED-UV light having a wavelength of 365 nm for 200 minutes to cause radical polymerization, whereby polymer chains were grown on the rubber surface. Accordingly, a desired gasket was prepared.
  • the surface roughness was measured contactless at four points (on the first peak) for each of the gasket base materials and gaskets using a laser microscope.
  • the average of the four Ra values was determined as the surface roughness Ra (the average of the center-line surface roughnesses Ra defined in JIS B0601-2001).
  • Friction resistance index Friction resistance of each example / Friction resistance of Comparative Example 1 ⁇ 100
  • the gasket prepared in each of the examples and comparative examples was inserted into a COP resin barrel of a syringe.
  • a solution of red food coloring in water was introduced into the barrel, and the barrel was sealed with a cap. After storage at 40°C for two weeks, one month, three months, and six months, the barrel was visually observed for liquid leakage.
  • Table 1 shows that the surfaces of the gaskets of the examples exhibited greatly reduced friction resistance and thus had good sliding properties. Moreover, the gaskets having a predetermined surface roughness or less also presented no particular problem with liquid leakage. In contrast, the gaskets of Comparative Examples 1 and 2 exhibited high resistance to sliding upon insertion into the barrel, and also had very poor sliding properties.
  • the gasket (after the immobilization of polymer chains) of Comparative Example 3 had a high surface roughness and exhibited some liquid leakage after three-month storage.
  • the gasket (after the immobilization of polymer chains) of Comparative Example 4 had a slightly high surface roughness and exhibited some liquid leakage after six-month storage.
  • the gasket of the present invention when used as a gasket of a syringe plunger, provides sufficient resistance to liquid leakage while reducing the friction of the plunger against the syringe barrel, and therefore enables an easy and accurate treatment with the syringe.
  • the gasket has a small difference between static and kinetic coefficients of friction, and therefore it allows the start of pushing the plunger and the subsequent inward movement of the plunger to be smoothly carried out without pulsation.
  • a syringe barrel made of a thermoplastic elastomer in which polymer chains are formed on the inner surface the treatment with the syringe can also be facilitated as described above.

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  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Vascular Medicine (AREA)
  • Anesthesiology (AREA)
  • Biomedical Technology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Hematology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Sealing Material Composition (AREA)
  • Gasket Seals (AREA)
  • Infusion, Injection, And Reservoir Apparatuses (AREA)
  • Materials For Medical Uses (AREA)
EP17204605.4A 2017-03-14 2017-11-30 Joint Withdrawn EP3376076A1 (fr)

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JP2017048675A JP2018151028A (ja) 2017-03-14 2017-03-14 ガスケット

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Cited By (1)

* Cited by examiner, † Cited by third party
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EP3617565A4 (fr) * 2017-04-25 2020-12-30 NOK Corporation Élément d'étanchéité

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3268078B1 (fr) 2015-03-10 2020-11-04 Regeneron Pharmaceuticals, Inc. Système de perçage aseptique
MA49549B1 (fr) 2017-05-05 2022-05-31 Regeneron Pharma Auto-injecteur
JP7247608B2 (ja) * 2019-01-30 2023-03-29 住友ゴム工業株式会社 シリンジ用ガスケット
USD1007676S1 (en) 2021-11-16 2023-12-12 Regeneron Pharmaceuticals, Inc. Wearable autoinjector

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JP2004298220A (ja) 2003-03-28 2004-10-28 Terumo Corp プレフィルドシリンジ
WO2009030976A1 (fr) * 2007-09-03 2009-03-12 Becton Dickinson France Dispositif médical et revêtement lisse pour ce dispositif
WO2009030975A1 (fr) * 2007-09-03 2009-03-12 Becton Dickinson France Dispositif médical comprenant une chambre siliconée et un moyen de fermeture pourvu d'un revêtement
JP2010142573A (ja) 2008-12-22 2010-07-01 Coki Engineering Inc シリンジ用ガスケット及びその製造方法並びに該ガスケットを用いたプレフィルドシリンジ
EP2957310A1 (fr) * 2014-06-18 2015-12-23 Sumitomo Rubber Industries, Ltd. Joint destiné à être utilisé pour une seringue médicale et une telle seringue
EP2980458A1 (fr) * 2014-07-31 2016-02-03 Sumitomo Rubber Industries, Ltd. Joint
US20160101239A1 (en) * 2014-10-10 2016-04-14 Sumitomo Rubber Industries, Ltd. Gasket for prefilled syringe

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JP2002089717A (ja) * 2000-09-14 2002-03-27 Terumo Corp ガスケット
JP5717593B2 (ja) * 2011-08-31 2015-05-13 住友ゴム工業株式会社 プレフィルドシリンジ用ガスケットの成型金型
WO2016042912A1 (fr) * 2014-09-18 2016-03-24 住友ゴム工業株式会社 Procédé de modification de surface et corps élastique modifié en surface
WO2018092543A1 (fr) * 2016-11-15 2018-05-24 富士フイルム株式会社 Stratifié, son procédé de production et composition pour revêtement antibuée
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EP0879611A2 (fr) * 1997-05-22 1998-11-25 Daikyo Seiko, Ltd. Piston pour seringue et seringue préremplie
JP2004298220A (ja) 2003-03-28 2004-10-28 Terumo Corp プレフィルドシリンジ
WO2009030976A1 (fr) * 2007-09-03 2009-03-12 Becton Dickinson France Dispositif médical et revêtement lisse pour ce dispositif
WO2009030975A1 (fr) * 2007-09-03 2009-03-12 Becton Dickinson France Dispositif médical comprenant une chambre siliconée et un moyen de fermeture pourvu d'un revêtement
JP2010142573A (ja) 2008-12-22 2010-07-01 Coki Engineering Inc シリンジ用ガスケット及びその製造方法並びに該ガスケットを用いたプレフィルドシリンジ
EP2957310A1 (fr) * 2014-06-18 2015-12-23 Sumitomo Rubber Industries, Ltd. Joint destiné à être utilisé pour une seringue médicale et une telle seringue
EP2980458A1 (fr) * 2014-07-31 2016-02-03 Sumitomo Rubber Industries, Ltd. Joint
US20160101239A1 (en) * 2014-10-10 2016-04-14 Sumitomo Rubber Industries, Ltd. Gasket for prefilled syringe

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Publication number Priority date Publication date Assignee Title
EP3617565A4 (fr) * 2017-04-25 2020-12-30 NOK Corporation Élément d'étanchéité

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JP2018151028A (ja) 2018-09-27
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